S1  

Supporting Information

Synthesis, Structure and Gas-Phase Reactivity of the Mixed Silver Hydride Borohydride Nanocluster [Ag3(µ3-H)(µ3-BH4)LPh3]BF4 (LPh = bis(diphenylphosphino)methane). A. Zavras,a A. Ariafard,a-c G. N. Khairallah,a J. M. White,a Roger J. Mulder,d A. J. Canty,b and R. A. J. O’Haira,b a. School of Chemistry and ‡Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Melbourne, Victoria 3010, Australia. b. School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia. c. Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University, Shahrak Gharb, Tehran, Iran. d. CSIRO Manufacturing, Bayview Avenue, Clayton, VIC 3168, Australia

   

Electronic Supplementary Material (ESI) for Nanoscale.This journal is © The Royal Society of Chemistry 2015

  S2  

Contents

S3 ................................ Complete Citation for ref. 46 and description of conversion of NCE to voltage.

S4 ............................................................................................................................................... Figure S1

S5 ............................................................................................................................................... Figure S2

S6 ............................................................................................................................................... Figure S3

S7 ............................................................................................................................................... Figure S4

S8 ............................................................................................................................................... Figure S5

S9 ............................................................................................................................................... Figure S6

S10 ............................................................................................................................................. Figure S7

S11 ............................................................................................................................................. Figure S8

S12 ............................................................................................................................................. Figure S9

S13 ........................................................................................................................................... Figure S10

S14 ........................................................................................................................................... Figure S11

S15 ........................................................................................................................................... Figure S12

S16 ........................................................................................................................................... Figure S13

S17 ........................................................................................................................................... Figure S14

S18 ........................................................................................................................................... Figure S15

S19 ........................................................................................................................................... Figure S16

S20 ........................................................................................................................................... Figure S17

S21 ........................................................................................................................................... Figure S18

S22 ........................................................................................................................................... Figure S19

S24 ........................................................................................................................................... Figure S20

S24 ........................................................................................................................................... Figure S21

S25 ........................................................................................................................................... Figure S22

S26 ...................................... Cartesian coordinates and total energies for all of the calculated structures

  S3  

Complete citation for reference 46

Gaussian 09, revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.

Description of conversion of NCE to voltage for ERCID experiments.

The NCE was converted to an amplitude of the resonance excitation RF voltage (tick amp) (eq. 13). The tick amp slope and tick amp intercept are extracted from the normalised collision energy calibration file of the most recent calibration.

Amplitude (V)

= (NCE)%  ÷  30%((parent mass)(tick amp slope) + tick amp intercept)

(eq. 13)

   

  S4  

 

Figure S1: LTQ/FTICR high resolution ESI/MS of hydride/borohydride containing trinuclear silver(I) clusters. Comparison of measured (top panel) vs. simulated isotope ratios (bottom panel) and accurate mass determination for: (a) measured HR FT-ICR MS of [Ag3(H)(BH4)L3]+, 0.6 ppm error; (b) simulated isotope distribution of [Ag3(H)(BH4)L3]+; (c) measured HR FT-ICR MS of [Ag3(H)(BH4)L2]+ , 0.1 ppm error; (d) simulated isotope distribution of [Ag3(H)(BH4)L2]+; (e) measured HR FT-ICR MS of [Ag3(H)(BH4)L]+, 0.6 ppm error; (f) simulated isotope distribution of [Ag3(H)(BH4)L]+. L = dppm = bis(diphenylphosphino)methane. The most intense isotope peak is represented by the m/z value.

   

0

50

100

1488 1492 14960

50

100

1104 1107 1110 722 724 726

1493.12515 (c )1107.00317

722.88262

(b) 1493.12427

Relative  Intens

ity  (%)

(d)1107.00331

m/z

722.88303

(e )

(f)

(a )

  S5  

 

 

Figure S2: LTQ/FTICR high resolution ESI/MS of hydride/borohydride containing trinuclear silver(I) clusters. Comparison of measured (top panel) vs. simulated isotope ratios (bottom panel) and accurate mass determination for: (a) measured HR FT-ICR MS of [Ag3(H)(BH4)L3]+, 0.6 ppm error; (b) simulated isotope distribution of [Ag3(H)(BH4)L3]+. L = dmpm = bis(dimethylphosphino)methane. The most intense isotope peak is represented by the m/z value.

 

 

   

0

50

100

744 746 748 750 752

0

50

100

746.93356

746.93436(b)

Relative  Intens

ity  (%)

m/z

(a )

  S6  

Figure S3: LTQ ESI/MS in the negative ion polarity mode of an acetonitrile solution of 1. Solutions were diluted to ca. 50 µM in acetonitrile. The most intense isotope peak is represented by the m/z value.

   

50 60 70 80 90 1000

50

100

[10B F4]-‐

79

Relative  Intens

ity  (%)

m/z

[11B F4]-‐

80

  S7  

 

Figure S4: FT-IR spectra of: [Ag3(H)(BH4)L3]BF4 shown by the black line, NaBH4 shown by the red line and NaBF4 shown by the blue line. All spectra were collected from material as fine powders after mechanical grinding in a mortar and pestle and subsequently recorded using a Perkin-Elmer Spectrum one FTIR spectrometer operating in the diffuse reflectance mode. Each spectrum is an average of 32 scans.

   

500100015002000250030003500

80

90

 %  Trans

mittan

ce

cm -‐1

 [A g3(H )(B H

4)L

3]B F

4

 N aB H4

 N aB F4

100

  S8  

 

 

 

Figure S5: 1H NMR spectrum of 1 (400.1 MHz, CD3CN) at -15°C. Insets are the µ3-H (5.3 to 3.9 ppm) and µ3-BH4 (1.3 to -0.1 ppm) signals.

   

  S9  

 

Figure S6: 11B-decoupled 1H NMR spectrum of 1 (400.1 MHz, CD3CN) at -15°C. Insets are the µ3-H (5.3 to 3.9 ppm) and µ3-BH4 (1.3 to -0.1 ppm) signals.

   

  S10  

 

 

Figure S7: Overlay of the 11B-decoupled 1H (upper) and 1H (lower) NMR spectra of 1 (400.1 MHz, CD3CN) at -15°C of the µ3-BH4 (1.3 to -0.1 ppm) signals.

 

 

  S11  

 

Figure S8: 31P-decoupled 1H NMR spectrum of 1 (400.1 MHz, CD3CN) at -15°C. Insets are the µ3-H (5.3 to 3.9 ppm) and µ3-BH4 (1.3 to -0.1 ppm) signals.

   

  S12  

 

 

Figure S9: Overlay of the 31P-decoupled 1H (upper) and 1H (lower) NMR spectra of 1 (400.1 MHz, CD3CN) at -15°C of the µ3-H (5.3 to 3.9 ppm) signals.

 

 

  S13  

 

Figure S10: 1H-decoupled 31P NMR spectrum of 1 (162.0 MHz, CD3CN) at -15°C.

  S14  

 

Figure S11: 1H-decoupled 11B NMR spectrum of 1 (128.4 MHz, CD3CN) at -15°C.

 

  S15  

 

Figure S12: 1H-11B HSQC spectrum of 1 (400.1 MHz (1H), 128.4 MHz (11B), CD3CN) at -15°C.

  S16  

 

Figure S13: 19F-11B HSQC spectrum of 1 (376.5 MHz (19F), 128.4 MHz (11B), CD3CN) at -15°C.

 

 

   

  S17  

 

Figure S14: 1H-decoupled 19F NMR spectrum of 1 (376.5 MHz, CD3CN) at -15°C.

 

  S18  

 

Figure S15: 1H-decoupled 13C NMR spectrum of 1 (100.6 MHz, CD3CN) at -15°C.

 

  S19  

 

Figure S16: 1H NMR spectrum of 1 (400.1 MHz, CD3CN) recorded at temperatures from -15°C to +25°C; µ3-H (5.3 to 3.9 ppm)and H2 (4.56 ppm) signals.

  S20  

 

Figure S17: LTQ/FTICR high resolution ESI/MS of dihydride containing trinuclear silver(I) clusters. Comparison of measured (top panel) vs. simulated isotope ratios (bottom panel) and accurate mass determination for: (a) measured HR FT-ICR MS of [Ag3(H)2L2]+, 0.4 ppm error; (b) simulated isotope distribution of [Ag3(H)2L2]+; (c) measured HR FT-ICR MS of [Ag3(H)2L]+ , 0.5 ppm error; (d) simulated isotope distribution of [Ag3(H)2L]+. L = dppm = bis(diphenylphosphino)methane. The most intense isotope peak is represented by the m/z value.

 

0

50

100

1092 1095 10980

50

100

706 708 710 712 714

Relative  Intens

ity  (%)

1094.96964

(d)

(c )710.84930

(a )

(b)1094.97003

m/z

710.84965

  S21  

 

Figure S18: LCQ energy resolved CID of [Ag3(H)(BH4)L3]+. (a) CID spectrum at 0.92 volts. (b) branching ratio of products as a function of the activation amplitude used.

   

  S22  

 

Figure S19: LCQ energy resolved CID of [Ag3(H)(BH4)L2]+ . (a) CID spectrum at 0.90 volts. (b) branching ratio of products as a function of the activation amplitude used.

   

500 1000 15000

50

100

0.00

0.05

0.5

1.0

[A g3(H )(B H

4)L ]+  

723

(b)

Relative  Intens

ity  (%)

m/z

(a )

*

[Ag3(H )

2L

2]+  

1095

1.21.00.80.6

[A g3(H )

2L ]+  

709

Branc

hing

 Ratio

  [A g3(H )(B H

4)L

2]+  (1109)

 [A g3(H )

2L

2]+  (1095)

 [A g3(H )(B H

4)L ]+  (723)

 [A g3(H )

2L ]+  (709)

 [A g2(H )L ]+  (601)

 [A gL ]+  (491)  [H L ]+  (385)

[A g3(H )(B H

4)L

3]+

1493

[A g3(H )(B H

4)L

2]+

1109

0.4A c tiva tion  V olta ge  (V

p-‐p)

  S23  

 

Figure S20: LCQ energy resolved CID of [Ag3(H)(BH4)2]+ . (a) CID spectrum at 0.46 volts. (b) branching ratio of products as a function of the activation amplitude used.

   

600 800 10000

50

100

0.0

0.5

1.0

[A g3(H )(B H

4)L ]+

723

(b)

Relative  Intens

iy  (%)

m/z

*

[Ag3(H )

2L ]+

709

(a )[Ag

3(H )(B H

4)L

3]+

1493

0.60.50.4

Branc

hing

 Ratio

  [A g3(H )(B H

4)L ]+  (723)

 [A g3(H )

2L ]+  (709)

0.3A c tiva tion  V olta ge  (V

p-‐p)

  S24  

 

Figure S21: LCQ energy resolved CID of [Ag3(H)2L2]+ . (a) CID spectrum at 0.76 volts. (b) branching ratio of products as a function of the activation amplitude used.

   

400 600 800 1000 1200 14000

20

40

60

80

100

0.0

0.5

1.0

Relative  Intens

ity  (%)

m/z

*

[A g3(H )

2L ]+

709

[A g3(H )(B H

4)L

3]+

1493

[A g3(H )(B H

4)L

2]+

1109

[A g3(H )

2L2]+

1095

0.80.6

(b)

Branc

hing

 Ratio

  [A g3(H )2L 2]+  (1095)

 [A g3(H )(B H 4)L ]+  (723)

 [A g3(H )2L ]+  (709)

 [A g2(H )L ]+  (601)

 [A g L ]+  (491)

 [H L ]+  (385)

(a )

0.4A c tiva tion  V olta ge  (V

p-‐p)

  S25  

 

Figure S22: LCQ energy resolved CID of [Ag3(H)2L]+ . (a) CID spectrum at 1.04 volts. (b) branching ratio of products as a function of the activation amplitude used.

   

400 600 800 10000

50

100

0.0

0.5

1.0(a )

[A g3(H )

2L ]+

709

[Ag3(H )(B H

4)L

2]+

1109

[Ag3(H )(B H

4)L

3]+

1493

[H L ]+

385#

Relative  Intens

ity  (%)

m/z

*

[A g2(H )L ]+

601

#

[A g L ]+

491

(a )

0.4 0.6 0.8 1.0

Branc

hing

 Ratio

  [A g3(H )2L ]+  (709)

  [A g2(H )L ]+  (601)

  [A gL ]+  (491)

  [H L ]+  (385)

1.2A c tiva tion  V olta ge  (V

p-‐p)

  S26  

Cartesian coordinates and total energies for all of the calculated structures

[Ag3(H)(BH4)LMe3]+ E(M06/BS1) = -‐3109.492746  au  H(M06/BS1) = -‐3108.855609  au  G(M06/BS1) = -‐3108.984256  au  E(M06/BS2//M06/BS1) = -‐3113.708582  au   C -3.97746700 -0.36313700 0.79349200 H -5.06071400 -0.56258900 0.83956100 H -3.65612600 0.01562300 1.77535900 B -0.01623900 -0.02847300 2.20560000 H -1.05849000 0.53565300 1.81917100 H 0.00027600 -0.01769200 3.42388000 H -0.02278700 -0.01383300 -1.35399800 Ag -1.06204800 1.34923200 -0.32550700 P -3.59226200 0.97080100 -0.42509200 P -3.03609500 -1.93446300 0.49521000 H 0.00400400 -1.21247800 1.81790800 H 0.98892600 0.57697000 1.78816200 C 2.31496900 -3.22047900 0.86812600 H 3.04329300 -4.04521500 0.93438500 H 1.80713900 -3.12939600 1.83996700 Ag -0.63989200 -1.61381200 -0.33211900 P 1.00342900 -3.58570100 -0.38205800 P 3.17978900 -1.60684900 0.56194100 C 1.71114200 3.59430200 0.81033600 H 2.06750800 4.63661500 0.84823700 H 1.94298800 3.11680500 1.77401900 Ag 1.69206200 0.23636500 -0.38177300 P 2.60058300 2.62987200 -0.48998900 P -0.13575200 3.54306400 0.60947500 C 1.98159100 -3.85872700 -1.91465900 H 2.81740600 -4.55161000 -1.74270800 H 1.33280600 -4.27807800 -2.69269500 H 2.36650600 -2.90054600 -2.28658900 C 0.54158600 -5.30382900 0.07988200 H -0.17692100 -5.70397000 -0.64526600 H 1.41865600 -5.96416300 0.10767900 H 0.06600200 -5.30353400 1.06832400 C 4.76832500 -2.13670800 -0.19856900 H 5.42621000 -1.26411700 -0.29412300 H 5.27363200 -2.89219400 0.41806900 H 4.60415400 -2.54465100 -1.20213600 C 3.71554400 -1.14848700 2.25575900 H 4.25166400 -1.97044600 2.74862100 H 4.37728700 -0.27460700 2.19854900 H 2.83382900 -0.87070800 2.84661100 C 4.35035800 3.06317200 -0.12900600 H 5.00712400 2.62199700 -0.88833700 H 4.50421400 4.15061700 -0.11855700 H 4.63532400 2.65553600 0.84879100 C 2.26978900 3.61187300 -2.00724000 H 2.49360100 4.67750500 -1.85716000 H 2.88866900 3.23495700 -2.82991000

  S27  

H 1.21939000 3.49354400 -2.30264300 C -0.49938100 5.20563100 -0.08999700 H -1.58630100 5.34941400 -0.12807100 H -0.06304600 6.00095000 0.52907300 H -0.11262100 5.29475900 -1.11192700 C -0.69503000 3.73635600 2.34602800 H -0.21317200 4.59426500 2.83364800 H -1.78286300 3.88093600 2.36213900 H -0.46612600 2.81500000 2.89677200 C -4.78532400 2.27223300 0.08599200 H -4.73231700 3.11604200 -0.61243600 H -5.81723300 1.89675000 0.10820000 H -4.51885900 2.63903800 1.08516400 C -4.35354400 0.34476700 -1.97557500 H -5.36871300 -0.03970800 -1.80362700 H -4.40720600 1.15988100 -2.70716200 H -3.72784900 -0.44450900 -2.41073200 C -4.27905900 -2.98521500 -0.36256600 H -3.87516600 -3.99876800 -0.47347200 H -5.21592900 -3.04089400 0.20802900 H -4.49269200 -2.59729300 -1.36521800 C -3.02245800 -2.67006500 2.17655200 H -4.03207300 -2.72465100 2.60547200 H -2.60250400 -3.68262600 2.12371500 H -2.37707000 -2.06705000 2.82734800 [Ag3(H)(BH4)LMe2]+ E(M06/BS1) = -‐2228.000079  au  H(M06/BS1) = -‐2227.556000  au  G(M06/BS1) = -‐2227.659437  au  E(M06/BS2//M06/BS1) = -‐2232.072635  au   C 3.52543500 0.63553100 1.06518700 H 4.53836300 1.04914200 1.19727900 H 3.11809100 0.39356000 2.05811900 B -0.03440000 -0.92577500 2.19109600 H 1.10756600 -0.87279900 1.73871300 H -0.00810200 -0.98808400 3.39992700 H -0.23628300 -1.59905400 -1.64906500 Ag 1.37199300 -1.39535200 -0.85704800 P 3.59396400 -0.95238900 0.11909500 P 2.39794400 1.90376100 0.33540800 H -0.72275900 0.10002400 1.92976600 H -0.62276000 -1.94962400 1.77209700 C -3.61950400 1.06935800 0.56658100 H -4.60963700 1.50267600 0.35115200 H -3.36523200 1.31508600 1.60862800 Ag -0.00249100 1.14231700 0.26066400 P -2.32248100 1.85356800 -0.49234800 P -3.68005300 -0.78495500 0.43856000 Ag -1.36867200 -1.56625100 -0.14988600 C -2.85618400 1.46611200 -2.20256400 H -3.91876500 1.70247300 -2.35195600 H -2.26297000 2.06344400 -2.90503900 H -2.67395500 0.40890500 -2.43288900

  S28  

C -2.75123400 3.63165200 -0.34193300 H -2.10442300 4.22608800 -0.99782500 H -3.79805600 3.81338900 -0.62015300 H -2.59435600 3.96815700 0.68953500 C -5.17831500 -1.07728400 -0.57814000 H -5.37228200 -2.15452100 -0.63587700 H -6.05460400 -0.58513300 -0.13585000 H -5.03298000 -0.70737900 -1.59936600 C -4.22829200 -1.26656400 2.11808900 H -5.12783300 -0.71448000 2.42077500 H -4.44808200 -2.34050300 2.13600500 H -3.41988100 -1.07529800 2.83446300 C 4.10970800 -2.15233400 1.39918500 H 4.30936600 -3.12495400 0.93493000 H 5.01775100 -1.80939400 1.91205400 H 3.30147900 -2.27601800 2.12945500 C 5.09316900 -0.78680500 -0.92217400 H 5.96755400 -0.53129700 -0.30929900 H 5.28629000 -1.74056400 -1.42709300 H 4.95686300 -0.01946500 -1.69243900 C 3.22872200 2.35999900 -1.23586700 H 2.76246300 3.26730700 -1.63797900 H 4.29797900 2.55726500 -1.07723700 H 3.10646000 1.56788300 -1.98475500 C 2.75099000 3.35622300 1.39775400 H 3.82351800 3.59226100 1.39967700 H 2.19752500 4.22841500 1.03094800 H 2.42711900 3.15274000 2.42504900 [Ag3(H)2LMe3]+ E(M06/BS1) = -‐3082.838167  au  H(M06/BS1) = -‐3082.236005  au  G(M06/BS1) = -‐3082.360653  au  E(M06/BS2//M06/BS1) = -‐3087.044329  au   C 0.32077800 3.60658200 -1.30541800 H 0.56269200 4.65452300 -1.54764300 H 0.05207600 3.08814100 -2.23749500 H -0.68162100 0.38340600 -1.66917700 H -0.40724600 0.21797300 1.60544500 Ag -1.53893500 0.95984300 0.10344300 P -1.16343500 3.48804500 -0.20362100 P 1.81182700 2.74457500 -0.61277400 C 3.56395700 -1.84375700 -0.37535800 H 4.36368000 -2.58337100 -0.19899100 H 3.84549900 -1.25156400 -1.26019700 Ag 1.23470600 0.65865500 0.87829600 P 3.44651100 -0.65314100 1.04106900 P 1.97309700 -2.68717000 -0.80493500 C -3.70227300 -1.95544700 -0.26258500 H -4.50668000 -2.57878800 0.16464500 H -3.90067200 -1.84439800 -1.33993200 Ag -0.10627500 -1.25341400 -1.08134800 P -2.06705300 -2.81726200 -0.13106700 P -3.76334900 -0.24273300 0.45133000

  S29  

C 2.68673000 2.26834700 -2.16019900 H 3.69101900 1.89613500 -1.91954800 H 2.12792200 1.46313100 -2.65393000 H 2.78609100 3.11628200 -2.85145900 C 2.85147900 4.15410300 -0.03988500 H 2.39861600 4.64022900 0.83230700 H 3.83666600 3.77745200 0.26300800 H 2.98996500 4.90107300 -0.83326300 C -2.30362800 4.65938600 -1.04798700 H -2.58681800 4.26024600 -2.02899000 H -3.21715600 4.77850800 -0.45356100 H -1.84032500 5.64626900 -1.18326600 C -0.63298700 4.49104300 1.24513500 H 0.13055200 3.94651200 1.81518500 H -0.23827800 5.46958300 0.93646300 H -1.48738300 4.65208300 1.91295900 C -5.36774000 0.32896100 -0.24640200 H -5.64062200 1.29134100 0.20289600 H -5.27536200 0.47274900 -1.32911500 H -6.17110300 -0.39323700 -0.04645400 C -4.25044400 -0.54609600 2.19941200 H -3.39418500 -0.89658500 2.78593900 H -4.58391300 0.40234800 2.63803200 H -5.06996500 -1.27444200 2.27482400 C -1.93854700 -3.15510700 1.67561200 H -1.61826100 -2.24871400 2.20537200 H -2.88971900 -3.51524900 2.09302900 H -1.17695800 -3.92806700 1.84139400 C -2.54504100 -4.48676900 -0.75312900 H -2.81975600 -4.42967800 -1.81297400 H -1.69593400 -5.17577400 -0.66093700 H -3.39280200 -4.89912500 -0.18907100 C 1.72937400 -3.83788800 0.60854000 H 0.97886300 -4.58647300 0.32102400 H 2.65487800 -4.35999500 0.88914200 H 1.33599000 -3.28716900 1.47347800 C 2.53571600 -3.83950400 -2.12082300 H 3.37561600 -4.45913800 -1.77925400 H 1.70579600 -4.49507700 -2.41137600 H 2.84457300 -3.27421200 -3.00763700 C 5.05220900 0.23000000 0.86894200 H 5.18706500 0.91038400 1.71846400 H 5.89751400 -0.47095500 0.84175200 H 5.05912200 0.82869100 -0.05001400 C 3.80890700 -1.70244300 2.50761600 H 4.68520300 -2.34282900 2.33597400 H 4.01588700 -1.04835700 3.36322400 H 2.94828300 -2.32603100 2.77053600 [Ag3(H)2LMe2]+ E(M06/BS1) = -‐2201.358866  au  H(M06/BS1) = -‐2200.950546  au  G(M06/BS1) = -‐2201.049756  au  E(M06/BS2//M06/BS1) = -‐2205.421185  au  

  S30  

C -3.69818300 0.61344000 -0.67045800 H -4.69083200 1.04474900 -0.45772900 H -3.67123500 0.34775000 -1.73823700 H 0.50430200 -2.33522700 0.87657300 Ag -1.14213600 -1.69924800 0.49701000 P -3.48877300 -0.96307400 0.27340800 P -2.36871900 1.87889600 -0.42529300 H 0.44894700 -0.48196200 -1.94541600 C 3.57250000 1.27458000 0.07352800 H 4.36611600 1.69516400 0.71379200 H 3.71242000 1.68179500 -0.93941300 Ag -0.05519700 0.96620900 -0.86814000 P 1.90474800 1.85529900 0.64126600 P 3.76549500 -0.57118900 -0.06253200 Ag 1.43715800 -1.43947800 -0.57573300 C 1.80558800 1.21758900 2.36365000 H 2.70702700 1.46485500 2.94222400 H 0.93773100 1.67140900 2.85969600 H 1.65382300 0.13062800 2.36179900 C 2.24496300 3.63869400 0.93792000 H 1.35902700 4.11364500 1.37699300 H 3.09254400 3.77410600 1.62330200 H 2.46874200 4.14455600 -0.00833500 C 4.56591100 -1.01039600 1.53133100 H 4.87201100 -2.06265600 1.49972200 H 5.45300500 -0.39004800 1.71801200 H 3.86074000 -0.89515900 2.36176000 C 5.17975500 -0.68769300 -1.22701900 H 6.01896600 -0.06317600 -0.89290800 H 5.51815300 -1.72847100 -1.28964000 H 4.86842800 -0.37064800 -2.22872000 C -4.59534800 -2.09970400 -0.64187200 H -4.67105300 -3.05241000 -0.10502700 H -5.59979400 -1.66810900 -0.74385900 H -4.18603500 -2.30155500 -1.63810800 C -4.42248400 -0.67560000 1.82480000 H -5.44016400 -0.32390800 1.60860900 H -4.48781500 -1.61850400 2.38040800 H -3.91627800 0.05558900 2.46443400 C -2.60358200 2.41457900 1.31673600 H -2.03609300 3.34063300 1.47617900 H -3.65909700 2.60891600 1.55330100 H -2.20178200 1.66125700 2.00696200 C -3.06998100 3.29626000 -1.35545600 H -4.07444900 3.55089600 -0.99209300 H -2.41980900 4.17119200 -1.24070100 H -3.12544200 3.05351900 -2.42273100  

[Ag3(H)(BH4)LMe]+ E(M06/BS1) = -‐1346.503099  au  H(M06/BS1) = -‐1346.252796  au  G(M06/BS1) = -‐1346.328975  au  E(M06/BS2//M06/BS1) = -‐1350.434988  au  

  S31  

C 2.77304200 0.44787800 -0.70082800 H 3.84707500 0.61820200 -0.51927800 H 2.59451000 0.58715900 -1.77755000 B -3.00308700 1.72117500 -0.55017900 H -2.49878700 2.03314500 0.55214400 H -3.68305700 2.65193700 -0.88278900 H -1.76354300 -2.07393000 0.60169200 Ag -0.62439200 1.58915600 -0.21635500 P 1.77580900 1.73168200 0.17333300 P 2.33871100 -1.30282300 -0.29713400 H -2.22756900 1.49915500 -1.51097700 H -3.84580500 0.78856700 -0.42172500 Ag -0.05758400 -1.62705800 0.17695000 Ag -2.71306200 -0.63870500 0.11998900 C 2.57892800 3.28527100 -0.35670800 H 2.10385300 4.13446000 0.14803200 H 3.64810500 3.27687400 -0.10771500 H 2.46061400 3.42276100 -1.43748000 C 2.25740400 1.57696700 1.93091900 H 3.34975700 1.53883400 2.04024200 H 1.88257500 2.45016900 2.47826000 H 1.80673900 0.68712100 2.38712900 C 3.47537900 -1.75476600 1.06441200 H 3.37805400 -2.82707300 1.27081400 H 4.51608800 -1.54519300 0.78429300 H 3.23211000 -1.21237200 1.98442100 C 3.01622600 -2.22316400 -1.72417000 H 4.07510000 -1.97656000 -1.87547300 H 2.92754200 -3.30023300 -1.54094700 H 2.45515700 -1.98435300 -2.63438800 [Ag3(H)2 LMe]+ E(M06/BS1) = -‐1319.874473  au  H(M06/BS1) = -‐1319.659579  au  G(M06/BS1) = -‐1319.730716  au  E(M06/BS2//M06/BS1) = -‐1323.792176  au   C 2.57420300 0.00000700 -0.73664800 H 3.67526200 0.00001300 -0.66019700 H 2.32387200 0.00000100 -1.80881400 H -2.36307400 -1.81378300 0.01483500 Ag -0.53275500 1.75070900 -0.01074100 P 1.92552200 1.59422200 -0.05709700 P 1.92553700 -1.59421200 -0.05708800 H -2.36309000 1.81376400 0.01491800 Ag -0.53273900 -1.75070600 -0.01073800 Ag -2.69224700 -0.00001100 0.01999200 C 2.79443600 2.80749200 -1.11634200 H 2.57080200 3.82279000 -0.76902100 H 3.88047900 2.65173500 -1.07689100 H 2.45488800 2.72097600 -2.15454300 C 2.76480000 1.79666000 1.55632200 H 3.83696200 1.57353000 1.47327800 H 2.64987000 2.83740000 1.88245900 H 2.31630400 1.16017600 2.32584800

  S32  

C 2.76484300 -1.79665700 1.55631400 H 2.64993400 -2.83740500 1.88243700 H 3.83700200 -1.57351100 1.47325500 H 2.31635300 -1.16019200 2.32585700 C 2.79442800 -2.80747700 -1.11635500 H 3.88047100 -2.65171300 -1.07694100 H 2.57081200 -3.82277600 -0.76902300 H 2.45484500 -2.72096900 -2.15454600 [Ag3(H)(BH4)]+ E(M06/BS1) = -‐464.9514358  au  H(M06/BS1) = -‐464.896099  au  G(M06/BS1) = -‐464.945194  au  E(M06/BS2//M06/BS1) = -‐468.728454  au   B -1.61211900 0.10699200 -0.00489400 H -2.16990200 -0.32646200 -1.03259000 H -1.19496000 1.22137900 -0.32689900 H 2.43333200 1.11782800 -0.06039000 Ag -3.95820800 -0.19732000 -0.00008400 H -2.24649000 0.29880400 1.05155600 H -0.82921000 -0.80479600 0.29407400 Ag 3.46187400 -0.33977700 -0.00008400 Ag 0.75309700 0.49365700 0.00226800 LMe E(M06/BS1) = -‐881.4273069  au  H(M06/BS1) = -‐881.235789  au  G(M06/BS1) = -‐881.285286  au  E(M06/BS2//M06/BS1) = -‐881.5738711  au   C 0.00312500 -0.73330400 0.21312300 H 0.02496600 -0.55105100 1.30301000 H -0.08841400 -1.82033900 0.06500200 P 1.60005000 -0.22672900 -0.60293900 P -1.51487300 0.04014800 -0.55846900 C 2.76542600 -0.91358000 0.67191400 H 3.79286800 -0.60506400 0.44095300 H 2.51732700 -0.57276300 1.68770600 H 2.73496900 -2.01000900 0.65393000 C 1.67505000 1.54994600 -0.06831800 H 1.42201600 1.67762900 0.99508700 H 2.69123100 1.93075000 -0.23174800 H 0.99595300 2.16149400 -0.67515400 C -1.78265900 1.44741400 0.62506000 H -2.77811600 1.87600600 0.45220500 H -1.72101100 1.12070800 1.67369900 H -1.04700500 2.24374800 0.46185500 C -2.77624600 -1.11506200 0.16918500 H -2.63021100 -1.25381900 1.25037100 H -3.78492300 -0.71741500 0.00085400 H -2.71546500 -2.09365600 -0.32244800  

BH3

  S33  

E(M06/BS1) = -‐26.582141  au  H(M06/BS1) = -‐26.551922  au  G(M06/BS1) = -‐26.574995  au  E(M06/BS2//M06/BS1) = -‐26.594077  au  E(B3LYP-D3BJ/BS2//M06/BS1) = -‐26.625207  au   B 0.00015600 0.00001000 -0.00003800 H -0.60766600 -1.02353700 0.00006300 H -0.58345700 1.03747200 0.00006300 H 1.19034500 -0.01398600 0.00006300 [Ag3(H)(BH4)LPh3]+ E(M06/BS1) = -‐5408.503573  au  H(M06/BS1) = -‐5407.186337  au  G(M06/BS1) = -‐5407.398341  au  E(M06/BS2//M06/BS1) = -‐5413.533698  au  E(B3LYP-D3BJ/BS2//M06/BS1) = -‐5416.591986  au   C 3.68616500 -1.26909300 0.99319100 H 4.73727500 -1.58118000 1.08180400 H 3.22382100 -1.31528500 1.99024600 B -0.01174500 0.05997400 2.42879100 H 0.60064700 -0.92112200 1.96641200 H 0.10944700 0.02953700 3.64241500 H -0.18314400 0.04741100 -1.12840100 Ag 0.26851600 -1.61287500 -0.15355400 P 2.68759200 -2.38501800 -0.09298800 P 3.55578000 0.50306400 0.43824400 H 0.47855000 1.12213100 2.01083200 H -1.22982300 -0.01338300 2.16571600 C -0.70620700 3.91417200 1.13768300 H -0.91230300 4.98564200 1.28210700 H -0.37137500 3.48589300 2.09484500 Ag 1.16606800 1.14814000 -0.19344100 P 0.68874000 3.63340000 -0.04370100 P -2.22933300 2.95611900 0.69661900 C -3.01246900 -2.73664000 1.06209500 H -3.77919200 -3.52442500 1.09966900 H -2.88059000 -2.33314100 2.07670300 Ag -1.74578700 0.53699100 0.08171100 P -3.50855800 -1.31498500 -0.01542400 P -1.36390200 -3.42623400 0.53515200 C 4.10294900 1.42079000 1.92423300 C 5.13202000 2.36496900 1.87870200 C 3.38614500 1.24264900 3.11530300 C 5.46195100 3.09489500 3.01673900 H 5.67917300 2.53485800 0.95209300 C 3.72583700 1.97012600 4.24934400 H 2.53907900 0.55464500 3.15850200 C 4.76894800 2.89193400 4.20506100 H 6.26675200 3.82711400 2.96959800 H 3.16845000 1.81552300 5.17163600 H 5.03493600 3.45936100 5.09567100 C 4.91370300 0.68392400 -0.76707200

  S34  

C 6.23494800 0.33434100 -0.46269200 C 4.61259400 1.17679400 -2.03830900 C 7.23501200 0.47805800 -1.41509900 H 6.48593400 -0.03478500 0.53307700 C 5.61482700 1.31688100 -2.99453500 H 3.58077500 1.44459900 -2.27819300 C 6.92370500 0.96677600 -2.68296200 H 8.26140700 0.21057300 -1.16996400 H 5.37075200 1.69652300 -3.98509800 H 7.70823900 1.07827700 -3.42946700 C 2.02529800 4.68113300 0.63308400 C 3.00677100 5.15915200 -0.24306200 C 2.15791500 4.92253400 2.00299300 C 4.08622300 5.88848400 0.24140300 H 2.91551800 4.97092400 -1.31435100 C 3.24087900 5.65234500 2.48351100 H 1.42233500 4.54001700 2.71032900 C 4.20143900 6.14238400 1.60542100 H 4.83529700 6.26800700 -0.45151300 H 3.33285500 5.83526200 3.55287900 H 5.04404600 6.71862800 1.98391100 C 0.19155600 4.47891200 -1.58253800 C -0.20035900 5.82191600 -1.60310300 C 0.20808800 3.74891700 -2.77314200 C -0.57740900 6.42007300 -2.79796700 H -0.20016700 6.40627600 -0.68154600 C -0.16204000 4.35224500 -3.97271100 H 0.50662400 2.69815600 -2.75247200 C -0.55594900 5.68546700 -3.98280400 H -0.88227800 7.46495200 -2.80979700 H -0.14405400 3.77920000 -4.89813400 H -0.84653600 6.15967900 -4.91873500 C -3.09858000 3.99456300 -0.53062800 C -3.58812500 5.26678400 -0.21721200 C -3.28137300 3.48410900 -1.81734200 C -4.24207600 6.01929500 -1.18447000 H -3.47015000 5.66357600 0.79275800 C -3.93960700 4.23776900 -2.78507100 H -2.90276300 2.48657200 -2.05650700 C -4.41648600 5.50496600 -2.46810500 H -4.62547500 7.00754700 -0.93649800 H -4.07747100 3.83420600 -3.78678500 H -4.93405400 6.09482300 -3.22268200 C -3.26048400 3.10490400 2.19757000 C -4.43262900 2.34027700 2.23163400 C -2.94391900 3.91561500 3.28906000 C -5.27616000 2.39666000 3.33337400 H -4.69208900 1.69636600 1.38727500 C -3.78504000 3.96088400 4.39773500 H -2.03760200 4.52013300 3.28607100 C -4.95037100 3.20350500 4.42099400 H -6.18535800 1.79773500 3.34223300 H -3.52568000 4.59190500 5.24594100 H -5.60519100 3.23854900 5.28972900 C -5.21514800 -0.92215300 0.50530500 C -5.93289000 -0.02737900 -0.29999800

  S35  

C -5.78213700 -1.36735000 1.70045200 C -7.19897800 0.39976600 0.07666000 H -5.49006600 0.34122000 -1.22855600 C -7.05182400 -0.93415200 2.07829300 H -5.24099700 -2.05498900 2.34890700 C -7.76137100 -0.05375000 1.26935600 H -7.74955200 1.09057400 -0.55909800 H -7.48646300 -1.29246400 3.00997400 H -8.75356200 0.28117700 1.56601400 C -3.72825800 -2.06346900 -1.66957200 C -4.58016600 -3.15373200 -1.87967800 C -3.00471800 -1.53931200 -2.74350200 C -4.68569800 -3.72478000 -3.14074900 H -5.16037300 -3.56280000 -1.05070300 C -3.12232200 -2.10430100 -4.01147800 H -2.33551100 -0.69210500 -2.57678400 C -3.95594600 -3.19976600 -4.20676900 H -5.33945000 -4.58128400 -3.29560900 H -2.56018300 -1.68799400 -4.84571300 H -4.04597100 -3.64606500 -5.19589900 C -0.76322500 -4.27052000 2.04131100 C -0.34249400 -5.60283100 2.03515800 C -0.59617200 -3.50266400 3.20174700 C 0.19757900 -6.16969100 3.18592200 H -0.43202800 -6.20325600 1.13025700 C -0.05994500 -4.07609700 4.34754400 H -0.86003000 -2.44351500 3.21016700 C 0.33105900 -5.41297100 4.34436800 H 0.51382700 -7.21170900 3.17305300 H 0.05641500 -3.47126400 5.24499600 H 0.74821300 -5.86129100 5.24454100 C -1.80201900 -4.74379100 -0.64796600 C -2.65540100 -5.80229300 -0.31308500 C -1.28704500 -4.66511400 -1.94377400 C -2.97893200 -6.76738900 -1.25848200 H -3.05671900 -5.88161800 0.69863000 C -1.61766300 -5.62812200 -2.89282600 H -0.64090200 -3.82661200 -2.21551700 C -2.45866700 -6.68080000 -2.54886500 H -3.63570400 -7.59260900 -0.98896100 H -1.21881700 -5.55223200 -3.90304300 H -2.71307700 -7.43801300 -3.28848700 C 3.55992900 -2.37400700 -1.69839200 C 4.90541000 -2.73875800 -1.81168000 C 2.85448200 -1.98592500 -2.84005700 C 5.53802800 -2.69951600 -3.04692800 H 5.45974600 -3.06181100 -0.92887800 C 3.48721700 -1.95733600 -4.08087600 H 1.80485000 -1.69530900 -2.74859800 C 4.82811900 -2.31079300 -4.18202200 H 6.58776400 -2.97608700 -3.12790000 H 2.93068400 -1.65919800 -4.96782800 H 5.32519700 -2.28766200 -5.15035300 C 2.98613100 -4.06566100 0.55590100 C 2.53253500 -5.13564800 -0.22660900 C 3.54936000 -4.32680100 1.80618900

  S36  

C 2.66784900 -6.44239500 0.22156300 H 2.07964600 -4.94369700 -1.20213500 C 3.67111100 -5.63869700 2.25861400 H 3.90124600 -3.51211300 2.43795600 C 3.24168900 -6.69631500 1.46588100 H 2.32660800 -7.26676500 -0.40258000 H 4.11527800 -5.83079800 3.23388600 H 3.34852400 -7.72067000 1.81896900 [Ag3(H)(BH4)LPh2]+ E(M06/BS1) = -‐3760.671618  au  H(M06/BS1) = -‐3759.774952  au  G(M06/BS1) = -‐3759.936572  au  E(M06/BS2//M06/BS1) = -‐3765.285290  au  E(B3LYP-D3BJ/BS2//M06/BS1) = -‐3767.347609  au   C 3.50633200 -0.16415800 1.16098600 H 4.50558400 0.20280000 1.43647600 H 3.06990300 -0.67696200 2.03106200 B -0.09044200 -1.80449600 2.00925600 H 0.97953200 -1.71979500 1.39348600 H 0.15860500 -2.12968900 3.15045600 H -0.30582100 -1.99452100 -1.90040300 Ag 1.30411100 -1.77829600 -1.11211100 P 3.58069400 -1.41426400 -0.20091700 P 2.35811700 1.23837100 0.78046400 H -0.71625900 -0.71517100 2.09309000 H -0.83078300 -2.66748900 1.49731100 C -3.57384200 0.57284400 0.92671600 H -4.52699500 1.12166300 0.92678800 H -3.23108300 0.47754500 1.96834400 Ag -0.00302300 0.46594100 0.49790900 P -2.24349400 1.51704400 0.04495300 P -3.75168400 -1.15269500 0.25755500 Ag -1.47459800 -1.98158200 -0.42908900 C -2.23596700 3.13154100 0.90147700 C -2.79627800 4.29777000 0.37754200 C -1.56663000 3.18177100 2.13237400 C -2.69705400 5.49474600 1.08157400 H -3.30047100 4.27898300 -0.58794500 C -1.47699200 4.37613600 2.83529200 H -1.09969500 2.28031800 2.54170600 C -2.04232300 5.53510200 2.30784900 H -3.13150300 6.40195600 0.66571400 H -0.95523200 4.40435400 3.79010300 H -1.96540500 6.47434300 2.85226100 C -4.54108400 -2.06863100 1.61817400 C -4.28027300 -3.43981700 1.69806100 C -5.39164800 -1.47635300 2.55800100 C -4.87344200 -4.21147100 2.69025300 H -3.59660600 -3.90226200 0.98422100 C -5.97759400 -2.24906000 3.55409400 H -5.59787600 -0.40615500 2.52364300 C -5.72182200 -3.61592900 3.61827700 H -4.66213500 -5.27732400 2.74613500

  S37  

H -6.63598700 -1.78218200 4.28415800 H -6.18056000 -4.21746600 4.40050400 C -2.89016700 1.78169900 -1.63356300 C -4.20645700 2.19587000 -1.87450700 C -2.04325900 1.52388200 -2.71503000 C -4.66088600 2.35554200 -3.17688500 H -4.88709900 2.38248000 -1.04272300 C -2.49953500 1.68775200 -4.01969800 H -1.02743200 1.16952700 -2.53092200 C -3.80648300 2.10442300 -4.24892000 H -5.68826100 2.66602600 -3.35759900 H -1.83558700 1.48102600 -4.85675000 H -4.16741600 2.22752700 -5.26842900 C -5.00819900 -1.00239300 -1.05913100 C -6.33469700 -0.64979100 -0.78765300 C -4.61316400 -1.23137600 -2.37907800 C -7.24600400 -0.51252300 -1.82701700 H -6.66364900 -0.49913100 0.24162600 C -5.52816300 -1.09532900 -3.41845600 H -3.57677500 -1.50100400 -2.59303400 C -6.84289300 -0.73548000 -3.14264000 H -8.27844700 -0.24413400 -1.61040000 H -5.21175900 -1.27235400 -4.44487700 H -7.56221400 -0.63447400 -3.95340700 C 4.24925600 -2.91123500 0.59065400 C 4.03118200 -4.12884200 -0.06270800 C 4.97711600 -2.89325000 1.78398000 C 4.54255400 -5.30902300 0.46283500 H 3.45283000 -4.15281600 -0.98860800 C 5.48051500 -4.07763700 2.31140800 H 5.15538100 -1.95820200 2.31475800 C 5.26597300 -5.28347800 1.65175400 H 4.36702400 -6.25203900 -0.05083300 H 6.04253100 -4.05744500 3.24303200 H 5.65934400 -6.20867500 2.06818600 C 4.89314500 -0.81537500 -1.31439800 C 6.22791200 -0.76554400 -0.89691300 C 4.55261500 -0.38235600 -2.59685100 C 7.20478300 -0.26859200 -1.74977300 H 6.50591200 -1.13311500 0.09216400 C 5.53247900 0.11948600 -3.44770000 H 3.51346900 -0.43386000 -2.92690700 C 6.85618700 0.17618300 -3.02381000 H 8.24350500 -0.23826600 -1.42626100 H 5.26152300 0.45958200 -4.44546500 H 7.62409300 0.55992500 -3.69311500 C 2.42836800 2.23641000 2.30834200 C 2.94984700 3.53045600 2.35306900 C 1.84986700 1.68247600 3.45927500 C 2.90790500 4.25728800 3.54007200 H 3.38707500 3.97670300 1.46041600 C 1.82243200 2.40830500 4.64349700 H 1.41507900 0.67982000 3.43228600 C 2.35158300 3.69728700 4.68480400 H 3.31750200 5.26524300 3.56876600 H 1.38362900 1.96745200 5.53683200

  S38  

H 2.32765200 4.26588400 5.61259900 C 3.18420200 2.19033800 -0.53043000 C 4.55472400 2.47594100 -0.50118800 C 2.41660700 2.62015000 -1.61631200 C 5.14596800 3.16978300 -1.54850300 H 5.16665800 2.15384100 0.34253900 C 3.00861700 3.32483700 -2.66050600 H 1.34827800 2.39669500 -1.63784800 C 4.37233600 3.59514600 -2.62751100 H 6.21361300 3.37956600 -1.52476800 H 2.40416900 3.65944500 -3.50134100 H 4.83894400 4.13942500 -3.44656700  [Ag3(H)2LPh3]+ E(M06/BS1) = -‐5381.859998  au  H(M06/BS1) = -‐5380.577766  au  G(M06/BS1) = -‐5380.779571  au  E(M06/BS2//M06/BS1) = -‐5386.877760  au  E(B3LYP-D3BJ/BS2//M06/BS1) = -‐5389.905173  au   C 3.22338900 1.25157600 1.49458000 H 4.09480700 1.76418500 1.92775500 H 2.61113300 0.83753500 2.30755900 H 0.72527500 -0.71182700 1.53989600 H 0.58782500 -0.34978800 -1.86190900 Ag 1.46324900 -1.24625100 -0.33328900 P 3.68397700 -0.18478000 0.41375800 P 2.17043000 2.46226900 0.54625900 C -2.51825100 2.96031300 0.49444200 H -3.44946900 3.53894500 0.39497100 H -1.89791700 3.41391700 1.28424100 Ag 0.44364400 1.32152800 -1.08188100 P -1.50559300 3.00516500 -1.05531800 P -2.88105300 1.22905900 1.04202500 C -0.64743500 -4.02630400 0.71630100 H -1.01424900 -5.05930600 0.62173300 H -0.36366900 -3.86018300 1.76538400 Ag -0.97213000 -0.39410700 0.96449000 P -1.95744000 -2.77349600 0.31518000 P 0.92722800 -3.73595800 -0.24102700 C 1.19310500 3.30836700 1.84852000 C 0.96641800 4.68823400 1.79919700 C 0.49182800 2.54047800 2.79002300 C 0.07462500 5.28705100 2.68694100 H 1.48145700 5.30516600 1.06147100 C -0.39775200 3.14175200 3.67376300 H 0.61168400 1.45555600 2.81635100 C -0.60815000 4.51922200 3.62490700 H -0.08407900 6.36352400 2.63890400 H -0.93627500 2.52960400 4.39769000 H -1.30574900 4.98877000 4.31744700 C 3.38287500 3.70029800 -0.03032700 C 4.19853200 4.42739700 0.84481900 C 3.51429000 3.89403100 -1.40669700 C 5.13018200 5.32927300 0.34587300

  S39  

H 4.09367900 4.29547300 1.92299400 C 4.44967900 4.79590300 -1.90641100 H 2.89337700 3.31479900 -2.09291500 C 5.25597200 5.51340200 -1.03008300 H 5.75930400 5.89407900 1.03160700 H 4.55281100 4.93048300 -2.98188800 H 5.98809900 6.21936200 -1.41820900 C -1.01434000 4.76167800 -1.18964000 C 0.04746300 5.04615800 -2.05533100 C -1.59192300 5.80217400 -0.45817700 C 0.51871000 6.34618700 -2.19389300 H 0.51569200 4.23620800 -2.62037500 C -1.11173500 7.10176400 -0.58793500 H -2.41285700 5.60533000 0.23122000 C -0.05761800 7.37530600 -1.45406200 H 1.34591600 6.55565700 -2.86969200 H -1.56635600 7.90488600 -0.01015500 H 0.31670000 8.39259900 -1.55150600 C -2.72400200 2.73863000 -2.39384200 C -3.93192800 3.44034700 -2.45986300 C -2.43221000 1.78230800 -3.36949400 C -4.83978100 3.17516200 -3.47660400 H -4.16613200 4.20407500 -1.71643800 C -3.33896300 1.52338000 -4.39339500 H -1.49400300 1.22450300 -3.31165000 C -4.54338500 2.21639000 -4.44411300 H -5.78006400 3.72161500 -3.52092700 H -3.10368200 0.77614700 -5.14967800 H -5.25544200 2.01402900 -5.24226000 C -4.32399400 0.73279900 0.03700300 C -5.63665500 1.07157700 0.37437700 C -4.08312200 -0.03445700 -1.10579100 C -6.69131500 0.64213700 -0.42485600 H -5.83596300 1.65703300 1.27318200 C -5.13607000 -0.45307700 -1.91201100 H -3.06014300 -0.32187100 -1.35758400 C -6.44276000 -0.11899300 -1.56576300 H -7.71394900 0.90002100 -0.15477000 H -4.92825900 -1.05586500 -2.79637800 H -7.27370400 -0.45507200 -2.18357400 C -3.52545700 1.42301800 2.73620300 C -3.61835600 0.25780100 3.50702000 C -3.87496900 2.64993800 3.30546200 C -4.05522700 0.32108800 4.82447900 H -3.34427200 -0.70858500 3.07422400 C -4.30030400 2.71181000 4.62985700 H -3.80298500 3.56981900 2.72487000 C -4.38867300 1.54963600 5.39002200 H -4.12581800 -0.59376600 5.41066600 H -4.56497200 3.67275400 5.06806300 H -4.71817700 1.60182600 6.42607400 C -3.31219200 -3.13955600 1.49167800 C -4.61524600 -2.72005700 1.18438200 C -3.04749100 -3.61497500 2.78100600 C -5.62359300 -2.78926500 2.13822800 H -4.84453300 -2.32892000 0.19166800

  S40  

C -4.06025100 -3.68197500 3.73460700 H -2.04563800 -3.94408100 3.05554800 C -5.35013200 -3.26893400 3.41693600 H -6.62887400 -2.46177200 1.87784500 H -3.83839500 -4.06706100 4.72872200 H -6.14143300 -3.32230200 4.16249200 C -2.57229400 -3.31642700 -1.31964600 C -3.47200100 -4.37493500 -1.47965200 C -2.08618800 -2.65008600 -2.45031200 C -3.88859400 -4.75238600 -2.75113700 H -3.85369400 -4.89991400 -0.60328000 C -2.49322500 -3.04135100 -3.72266100 H -1.36728600 -1.83355900 -2.33408200 C -3.40098200 -4.08568000 -3.87285400 H -4.59347800 -5.57369200 -2.86887000 H -2.09506900 -2.52999000 -4.59791100 H -3.72462400 -4.38820500 -4.86729500 C 2.13019500 -4.67691300 0.77213600 C 2.82416500 -5.79765900 0.31476000 C 2.41512900 -4.16948400 2.04780700 C 3.76914600 -6.41628700 1.13136100 H 2.62729700 -6.19514000 -0.68053800 C 3.34536900 -4.79752600 2.86373700 H 1.91866500 -3.26136000 2.39874800 C 4.02444900 -5.92502100 2.40637300 H 4.30189200 -7.29288900 0.76628100 H 3.56456000 -4.38757400 3.84849900 H 4.76297100 -6.41196600 3.04134100 C 0.71846500 -4.67979900 -1.78776900 C 0.17231700 -5.96730100 -1.83686300 C 1.12999000 -4.06687500 -2.97441800 C 0.04794100 -6.62998100 -3.05171500 H -0.14240300 -6.46702700 -0.91935300 C 1.00453100 -4.73085500 -4.19085400 H 1.53584300 -3.05364300 -2.93885300 C 0.46292100 -6.01096500 -4.22916000 H -0.37579700 -7.63219700 -3.08146100 H 1.32665400 -4.24456300 -5.11001000 H 0.36272800 -6.53257900 -5.17943500 C 4.83351800 0.55945700 -0.80260600 C 6.01600800 1.19574600 -0.40995200 C 4.51761300 0.47094800 -2.16004200 C 6.86752400 1.73836500 -1.36300400 H 6.27990400 1.25424900 0.64754600 C 5.37701200 1.00870600 -3.11638600 H 3.59015500 -0.02179600 -2.45995100 C 6.55006200 1.64022700 -2.71707100 H 7.78494700 2.23494900 -1.05187400 H 5.13153000 0.92780700 -4.17410000 H 7.22491000 2.05603000 -3.46346400 C 4.78662900 -1.20730200 1.45325300 C 5.29749000 -2.36377600 0.84969800 C 5.10600900 -0.93761400 2.78507700 C 6.14158300 -3.21176900 1.55151800 H 5.02658500 -2.60020400 -0.18201600 C 5.93838000 -1.80187300 3.49493700

  S41  

H 4.71481000 -0.04933400 3.28061400 C 6.46298000 -2.93197600 2.87851300 H 6.53655800 -4.10387300 1.06848200 H 6.18465100 -1.58115700 4.53231500 H 7.12029200 -3.60035200 3.43236600  Lph E(M06/BS1) = -‐1647.753043  au  H(M06/BS1) = -‐1647.335460  au  G(M06/BS1) = -‐1647.415099  au  E(M06/BS2//M06/BS1) = -‐1648.173935  au  E(B3LYP-D3BJ/BS2//M06/BS1) = -‐1649.152524  au   C -0.15652900 -1.16618900 -0.32843300 H -0.01965600 -1.01525600 0.75308800 H -0.48718000 -2.20281600 -0.48187100 P 1.43122900 -0.93731700 -1.28097900 P -1.50014200 -0.04756900 -1.01543400 C -2.98624000 -1.00570700 -0.47638100 C -4.00413700 -0.48090800 0.32459500 C -3.15925000 -2.28838500 -1.01298600 C -5.14361200 -1.22983100 0.60828400 H -3.90657600 0.52216100 0.73803000 C -4.29163200 -3.03932300 -0.72442100 H -2.40075400 -2.70524100 -1.67893700 C -5.28857200 -2.51225400 0.09249000 H -5.92152400 -0.80484000 1.24132800 H -4.40090100 -4.03758600 -1.14615000 H -6.17811700 -3.09761400 0.31961700 C -1.45242200 1.33328800 0.20555700 C -1.45638600 1.14268200 1.59304100 C -1.37363700 2.63548700 -0.29091500 C -1.37620600 2.22620600 2.45821800 H -1.53502800 0.13415500 2.00205000 C -1.29088500 3.72456100 0.57368100 H -1.35673300 2.79521600 -1.36977700 C -1.29037300 3.52070000 1.94809300 H -1.38207900 2.06334000 3.53517100 H -1.21822400 4.73296000 0.16837600 H -1.22481400 4.37010700 2.62661500 C 1.75308500 0.84945900 -0.94751900 C 1.97206100 1.36079600 0.33703300 C 1.72792000 1.73045000 -2.03084300 C 2.14983300 2.72362300 0.53239100 H 1.99669900 0.68192100 1.19117300 C 1.91429400 3.09792600 -1.83844100 H 1.55606700 1.33501700 -3.03289200 C 2.12342100 3.59361500 -0.55697600 H 2.29994500 3.11411700 1.53818800 H 1.89692700 3.77409700 -2.69206600 H 2.26492300 4.66265300 -0.40220800 C 2.64746700 -1.71013800 -0.13113300 C 3.99979500 -1.36830800 -0.26749900 C 2.30296500 -2.69393400 0.79988700 C 4.97222000 -1.97690400 0.51449300

  S42  

H 4.29113500 -0.60439300 -0.99028900 C 3.27865400 -3.30929600 1.58109100 H 1.26168800 -2.98994100 0.92542700 C 4.61432500 -2.95157100 1.44366300 H 6.01645700 -1.68974300 0.39916900 H 2.98827000 -4.07056100 2.30402000 H 5.37623700 -3.43074400 2.05631200  [Ag3(H)(BH4)LPh]+ E(M06/BS1) = -‐2112.843086  au  H(M06/BS1) = -‐2112.366417  au  G(M06/BS1) = -‐2112.471802  au  E(M06/BS2//M06/BS1) = -‐2117.045602  au   C 1.19804900 0.72864200 -1.23993400 H 2.09599000 1.36379400 -1.27561200 H 0.90555200 0.48283300 -2.27061100 B -4.56184100 -0.45392400 -0.73297900 H -4.23791100 0.23551400 0.25873100 H -5.61405600 -0.01354000 -1.10526500 H -1.84636300 -2.74206500 1.43493400 Ag -2.34489000 0.51184800 -0.68289100 P -0.20280200 1.65297600 -0.46555200 P 1.55043800 -0.87179200 -0.37385400 H -3.79336000 -0.44366400 -1.72539700 H -4.83131400 -1.65514200 -0.44645100 Ag -0.47539800 -1.86546000 0.61458000 Ag -3.28976100 -2.11208100 0.58705300 C 0.28827200 1.89051100 1.26738700 C 1.47473100 2.56566000 1.58107700 C -0.50642600 1.37191400 2.29368500 C 1.87011700 2.69274000 2.90493600 H 2.08899800 2.99382900 0.78741500 C -0.11047400 1.50800700 3.62199200 H -1.44634100 0.86707900 2.05576300 C 1.07978000 2.16076500 3.92380600 H 2.79612700 3.21085300 3.14647100 H -0.73693600 1.11087100 4.41790800 H 1.39053300 2.26807900 4.96131500 C -0.15267500 3.30395500 -1.22482800 C 0.40281100 3.52785100 -2.48725200 C -0.77452500 4.35583600 -0.54204500 C 0.34737200 4.79771900 -3.05331600 H 0.88247400 2.72074600 -3.04008800 C -0.82653500 5.62030100 -1.11331500 H -1.21144400 4.18867000 0.44367800 C -0.26547100 5.84176700 -2.36893000 H 0.78568300 4.96923100 -4.03431100 H -1.30771700 6.43586000 -0.57770200 H -0.30947900 6.83246700 -2.81630500 C 2.82253700 -0.48003700 0.86604700 C 4.04383700 0.09336500 0.49337700 C 2.57789700 -0.77303400 2.20889600 C 4.99762000 0.38522400 1.45912300 H 4.26251300 0.29657300 -0.55597600

  S43  

C 3.53635200 -0.48097400 3.17472200 H 1.62779800 -1.22159100 2.50685300 C 4.74261000 0.09994800 2.79984600 H 5.94828500 0.82599800 1.16597200 H 3.33820800 -0.71019900 4.21999200 H 5.49525100 0.32279600 3.55358500 C 2.34645500 -1.90127900 -1.64159300 C 2.20743200 -3.28853200 -1.53108000 C 3.11602400 -1.36532100 -2.68012000 C 2.83545500 -4.13024100 -2.44193500 H 1.60281900 -3.71385200 -0.72769100 C 3.73639200 -2.20997400 -3.59281400 H 3.23402800 -0.28670200 -2.78721100 C 3.59774300 -3.59036100 -3.47302800 H 2.72187900 -5.20821600 -2.35079300 H 4.33040500 -1.78925100 -4.40145700 H 4.08304800 -4.24827100 -4.19081000  [Ag3(H)2LPh2]+ E(M06/BS1) = -‐3734.032094  au  H(M06/BS1) = -‐3733.170615  au  G(M06/BS1) = -‐3733.326060  au  E(M06/BS2//M06/BS1) = -‐3738.636247  au   C -3.70899500 0.17538600 -0.68329400 H -4.59355000 0.59071100 -0.17550400 H -3.96686000 0.04274600 -1.74521000 H 0.56395700 -3.26033400 -0.42095000 Ag -1.02965100 -2.41577900 -0.50901000 P -3.29492100 -1.51973400 -0.05145700 P -2.31179300 1.39979600 -0.72520000 H 0.55303800 -0.79072300 -2.64175000 C 3.53231000 0.87882500 -0.47531700 H 4.33186400 1.38015500 0.09111600 H 3.58885700 1.22873000 -1.51816200 Ag -0.09794200 0.38924600 -1.37299300 P 1.84534600 1.39490200 0.11074700 P 3.75083500 -0.96603200 -0.52743900 Ag 1.57695200 -1.91989600 -1.40009100 C -2.92090900 2.62752600 -1.92777400 C -3.95780900 3.51188300 -1.61259300 C -2.34559200 2.65709000 -3.20110200 C -4.41662600 4.41107300 -2.56669900 H -4.39623200 3.50345800 -0.61348100 C -2.80891600 3.55901000 -4.15467500 H -1.53559500 1.96598700 -3.44671700 C -3.84246900 4.43375400 -3.83664400 H -5.22284000 5.09939200 -2.32047300 H -2.35989100 3.57930100 -5.14578800 H -4.20362100 5.14105600 -4.58087100 C -2.32625300 2.29038000 0.86679100 C -3.07817500 1.90800600 1.97809100 C -1.44615900 3.37713100 0.97727900 C -2.93415600 2.58239200 3.18925000 H -3.77880100 1.07718900 1.92138000

  S44  

C -1.32145200 4.05945000 2.17907600 H -0.85234700 3.68993200 0.11446100 C -2.05683900 3.65506700 3.29244100 H -3.51811400 2.26033000 4.05044200 H -0.63816600 4.90418800 2.24738200 H -1.94631200 4.18079500 4.23897000 C -4.63231600 -2.57991000 -0.68958100 C -4.40009900 -3.95973700 -0.66929100 C -5.85837800 -2.09721200 -1.15674300 C -5.38173400 -4.84372600 -1.09879900 H -3.44180300 -4.34445700 -0.31334300 C -6.83567600 -2.98539600 -1.59485900 H -6.06333200 -1.02706400 -1.18409600 C -6.59966000 -4.35592300 -1.56443800 H -5.19138600 -5.91477600 -1.07994100 H -7.78588000 -2.60283400 -1.96241300 H -7.36542900 -5.04708300 -1.91069500 C -3.59345000 -1.43472000 1.74780900 C -4.89003600 -1.30131100 2.25717600 C -2.50565900 -1.44887000 2.62433300 C -5.09102300 -1.15258300 3.62388700 H -5.74707500 -1.31978300 1.58221400 C -2.71132100 -1.31137500 3.99450000 H -1.49139500 -1.56889400 2.23432000 C -4.00052100 -1.15437500 4.49249800 H -6.10052700 -1.04789200 4.01661400 H -1.86107700 -1.34080300 4.67419300 H -4.16063100 -1.04962200 5.56397000 C 1.89590100 3.20592200 -0.16117100 C 2.08756900 4.13749900 0.86065900 C 1.63950300 3.65807200 -1.46254200 C 2.02648600 5.50070700 0.58319400 H 2.26581500 3.79919200 1.88146800 C 1.58498600 5.01907300 -1.73813300 H 1.47146200 2.93420400 -2.26535100 C 1.77350300 5.94248700 -0.71168900 H 2.17635600 6.22254800 1.38456500 H 1.38676800 5.36068000 -2.75237000 H 1.72200700 7.00871300 -0.92335800 C 1.85373400 1.18200300 1.92219500 C 2.98335600 1.37902100 2.72398600 C 0.64237400 0.83605100 2.52884700 C 2.89965800 1.23120700 4.10335300 H 3.94180800 1.64282800 2.27639700 C 0.55370800 0.70956600 3.91131700 H -0.24686500 0.67596300 1.91427700 C 1.68408800 0.90141600 4.69907700 H 3.78658300 1.37942900 4.71654400 H -0.40768500 0.47349000 4.36657400 H 1.62015000 0.79741000 5.78071300 C 5.28921600 -1.20082400 -1.47630100 C 5.48582600 -2.45819600 -2.05764400 C 6.26337100 -0.21125800 -1.63940000 C 6.64376700 -2.72701200 -2.77725900 H 4.72290000 -3.23070700 -1.94440900 C 7.41794300 -0.48037600 -2.36718100

  S45  

H 6.12754700 0.77709700 -1.19986700 C 7.60931300 -1.73674700 -2.93380300 H 6.78812000 -3.70839200 -3.22485100 H 8.17090200 0.29542600 -2.49316500 H 8.51276600 -1.94417100 -3.50393500 C 4.17722500 -1.38641300 1.20016200 C 5.44380900 -1.12580600 1.73242800 C 3.18872100 -1.94683100 2.01380300 C 5.71328700 -1.41342500 3.06538600 H 6.22846300 -0.71053700 1.09806500 C 3.45895500 -2.22570300 3.34966200 H 2.20106000 -2.15874500 1.59723200 C 4.72052900 -1.96294700 3.87406900 H 6.70418800 -1.22017900 3.47259000 H 2.68342900 -2.65742300 3.97994900 H 4.93602200 -2.19428100 4.91589800  [Ag3(H)2LPh]+ E(M06/BS1) = -‐2086.21344  au  H(M06/BS1) = -‐2085.773971  au  G(M06/BS1) = -‐2085.871002  au  E(M06/BS2//M06/BS1) = -‐2090.401324  au   C -1.12363400 0.17555400 1.31058300 H -2.19262400 0.37700400 1.47610700 H -0.66135700 0.00238500 2.29231300 H 2.94677600 -1.92045100 -1.44646500 Ag 2.15296200 1.44178600 0.51499900 P -0.30849100 1.64206700 0.52958900 P -0.93478900 -1.39337500 0.32988400 H 3.94983000 1.11588900 0.28373000 Ag 1.25822100 -1.65536900 -0.77041100 Ag 3.77694700 -0.47231100 -0.65781100 C -0.96337100 1.66486900 -1.16827500 C -2.33068500 1.85011300 -1.40797400 C -0.09777800 1.43853200 -2.24221100 C -2.82199400 1.79082400 -2.70495100 H -3.01205100 2.04298000 -0.57803700 C -0.59274200 1.38382900 -3.54263100 H 0.97264400 1.31087000 -2.06240700 C -1.95409000 1.55497400 -3.77066100 H -3.88660500 1.92577800 -2.88692800 H 0.08723600 1.21704200 -4.37551000 H -2.34279900 1.51486400 -4.78656900 C -1.03691100 3.08528000 1.36218800 C -0.93352300 4.32706700 0.72326200 C -1.61120900 3.00634800 2.63322800 C -1.41577200 5.47104600 1.34472800 H -0.48509500 4.39846800 -0.26893100 C -2.09093700 4.15757900 3.25126100 H -1.69009300 2.05299300 3.15484200 C -1.99525400 5.38693200 2.60878600 H -1.33873300 6.43254500 0.84138500 H -2.54150900 4.09005300 4.23932500 H -2.37136200 6.28488300 3.09454800

  S46  

C -1.11500700 -2.67665500 1.61130200 C -2.16523000 -3.59553800 1.62751100 C -0.10049800 -2.76437300 2.57343900 C -2.20754300 -4.58011600 2.61146900 H -2.94934600 -3.54919600 0.87310900 C -0.15353800 -3.74153300 3.55786100 H 0.74398900 -2.06967800 2.54884600 C -1.20948300 -4.65093400 3.57651500 H -3.02764600 -5.29506600 2.62101700 H 0.63503800 -3.80310100 4.30492700 H -1.24776600 -5.42212600 4.34291700 C -2.39430800 -1.45878500 -0.74610000 C -3.68835100 -1.25525700 -0.24852200 C -2.21218200 -1.71260700 -2.10683700 C -4.77965700 -1.30377200 -1.10598600 H -3.84922400 -1.07356200 0.81544900 C -3.30735800 -1.75849100 -2.96400800 H -1.20724900 -1.86586700 -2.50359100 C -4.58876600 -1.55499800 -2.46399300 H -5.78327500 -1.15238200 -0.71358100 H -3.15652800 -1.95291900 -4.02403800 H -5.44620900 -1.59407800 -3.13295600